Production of styrene from butadiene



Patented May-2.9., 1945 S. PATENT OFFICE PRODUCTION OFSTYREN FROM BUTADIENE Vanderveer Voorhees, Homewood, Ill., assigner to Standard Oil Company, Chicago, Ill., a corpo ration o! Indiana application May 2s, '1942, serieu No. 444,165

' 1 claim. (ci. zoo-6,69)

This invention relates to the preparation of styrene. Heretofore styrene o r phenylethylene has usually been obtained from the distillation of coal and vby various other pyrolytic processes.

' Styiene obtained from many of these sources is high temperaturein the presence of a contact catalyst to yield the desired styrene product. The principal reactions involved are substantially the following:

` :Capone-ormoni, butadiene p Three structural formulas are suggested for the butadiene dimer, inasmuch as the chemistry of this material is not thoroughly understood. The dimerization reaction may be carried out in various ways and it appears that the chemical charmagnesium oxide, activel silica, silica gel, or thorium oxide. The reaction conditions should be controlled to avoid polymerization to higher molecular weight products as far as possible. When using catalysts, for example, a short time of reaction should be provided. Also, it is desirable to limit the conversion per pass to about 50 to 75% of the butadiene, thereby avoiding continued polymerization and further reaction of butadiene with the dimer already formed in the process. T1

Where higher molecular Weight polymers are also desired, for example, in the polymerization of butadiene to elastomers, the reaction conditions may be controlled to produce both the high molecular weight polymer and the dimer. Such reactions are usually conducted in the liquid phase, for example, by treating liquid butadiene with various catalysts such as alkali metals and organic peroxides. This reaction may also be carried out; with the liquid butadiene in the form of an aqueous emulsion. The butadiene dimer `converted in the dimerization reaction, it may be separated from the dimer and recycled in the process until completely converted. This separa- '.tion'is easily made by distillation, taking advanaromatization of the dimer, the latter `is preferably subjected to the action of a contact aromatization groups of the periodic system. Suitable catalysts.v are the oxides of vanadium, chromium, molybacter of the dimer changes with different conditions used in itspreparation.

- One method of effecting conversion of-butadiene 'tothe dimer is. by heating butadiene at a temperature of about 250 to 500 C., preferably about -300 to 400 C. and at atmospheric pressure or a somewhat higher pressure, e. g., 5 to 10 atmospheres. A catalystmay be used to speed the retage of the difference in boiling point of the butadiene and- `the dimer, the former being a gas and the latter a liquid under ordinary conditions.

In the next step. of the process,.which involves catalyst at elevated temperature. For this purpose the dimer may be employed wi hout special purification although itis generali desirable to distill it and remove a small amount of high boiling polymers which may be present before charging it to the aromatization catalyst. The catalyst employed for this operation may be a metal or an -v oxide of a metal, preferably of the V, VI and VTII denum, tungsten or uranium or the VIII/group metals, nickel, cobalt, iron, platinum or palladium, or mixtures of-any of them with other metals or metal oxides.' When employing VIII group metals, .it is desirable to avoid contamination with sulfur which poisons the catalysts and decreases their eirectivenfe.

The catalyst may be supported on various subsupplying the heat necessary y zation reaction.l

stances which are generally porous materials of catalysts may conveniently beprepared by 'applying a solution of ammonium vanadate, ammonium chromate or ammonium molybdate .to active alumina, then -dryingand igniting the product, or salts of the catalytic'metals may be added to an alumina sol, for example, an alumina sol derived from the treatment of amalgamated aluminum metal with a weak acid solution, after which the sol maybe gelled and dried to give the desired catalyst. l

Other supporting substances which may be employed are silical gel, pumice, kieselguhr, asbestos, clays, preferably aidtreated clays such as bentonite, montmorillonite or fullers earth, charcoal, particularly activated charcoal, etc.

The temperature required for the aromatization reaction may vary considerably. generally within the range of about 450 to 800 C., depending on the activity of the particular catalyst employed, time of contact, pressure, and other factors. A suitable-temperature'when using chromium or molybdenum oxides and a contact time of about 1 to 10 seconds is about 500 to 600 C. The time of contact or reaction time employed in the aromatization ofthe dimer may vary from 0.1 second to 50 or 100 seconds and it is generally desirable to cool the products of the reaction rapidly in order to prevent secondary reactions, re-

as'raess catalysts Vof low activity and/or operating at.

lower temperatures.

Referring to the drawing, a stream of butadiene i's charged by line II) and pump II to tubular furnace I2 wherein the stream is heated to the desired dimerization temperature and -held at that temperature for a time suicient to effect formation Iof a substantial amount of dimer. The.

' vapors are conducted by line I3 vto fractionator Il wherein the products are separated into a dimer fraction withdrawn from trapout I5, a high boiling residue fraction withdrawn by line I'6 and an unchanged butadiene fraction-taken overhead by line I1 and conducted back to inlet line I 0. Redux for fractionation may be provided by a suitable reflux coil I 8. i'

Dimer withdrawn at I5 is forced by pump I9 through heater and thence by line 2| to aromatization chamber 22 wherein the vapors of the ,dimer are' brought into contact with the aromatization catalyst as described hereinabove. The

temperature of the reaction in 22 may be controlled by suitable heat exchange coils, not shown, distributed therein.4 The aromatized products,

chiefly styrene, are withdrawn by line 23 and conducted to fractionator y24l wherein the styrene is separated and withdrawn by trapout line 25.

A small amount of heavier products may be withdrawn from the bottom of the tower by line 28 while the hydrogen produced in the process and other gases may be withdrawn by line 21 and returned by pump 28 to heater 20 and thence to reaction chamber 22. Excess hydrogen and otherl light products may be withdrawn by line 29 if deducing the yield of styrene. Rapid chilling of sire'd and fresh hydrogen may be added to the into the hot reactionproducts leaving the aromatiztion apparatus. v

fThe activity and life of the catalyst in the aromatization reaction are generally improved by maintaining an atmosphere of hydrogen in contact with the catalyst, and hydrogen may be added to the dimer for this purpose. 'I'his hydrogen may be obtained by recycling hydrogenous gases produced in the aromatizationoperation itself.l About 1/2 to 5 mols of hydrogen per'mol' of dimer treated are sumcient and generally about 2 to 3 mols of hydrogen can be employed with satisfactory results. o Before introduction into the reactor the hydrogen may be heated to a high temperature substantially above the reactipn ,temperature as an additional means for for the aromati` The aromatization operation may be conducted at atmospheric or sub-atmospheric pressure or at somewhat elevated pressures of the order of 3 to 20 atmospheres. However, low pressures fa` cilitate the use of lshort contact time'and increase the yield of styrene by reducing secondary reactions. Pressures in the'range of about 0.2 to 2 atmospheres are therefore preferred. The time process by line 30, .especially when starting up.

Rapid cooling of the aromatization products from 22 may be eIIected by injecting quenching fluid into transfer line 2% by line 3|.

22 and the fractionator 2l to assist in reducing the temperature of the products below .the region in which styrene is lost through secondary re-v actions.

Any unchanged dimer which may be present in is then readily separated from other products and depolymerized to yield pure styrene. In general, a small amount of unchanged dimer which may be present in the styrene product obtained from aromatizer 22 s not objectionable for most pur- -poses for whic the styrene may be desired, for example, in the manufacture of synthetic rubber. However, `it is a characteristic of my process that the styrene produced is obtainable in a liigh state i of purity, generally requiring no further purification. A small amount of an antioxidant, for example catechol or butylaminophenol'may be' of contact of the dimer `with the aromatization` catalystmay be conveniently .indicatedby the space velocity expressed in volumes of liquid dimer per hour per volume of catalyst and in general, I 'may operate with space velocities of about 1 to l0 V/H/V, higher space velocities, e. g., 20

to 30 V/H/V, or even as high as 70 V/H/V being` employed for catalysts of very high activity operating at high temperatures, and 'somewhat lower space velocities, e. g., "as low vas 0.2, with` added to the styrene product to prevent oxidation and loss by polymerization in processing and in storage.

Although I have described and set forth rather specific operations inthe manufacture of styrene, it is intended that the invention be construed the invention are intended to be included. Thus. I may regulate conditions to obtain a transfer of Likewise a 40 cooler 32 may be interposed between the reactor prises polymerizing butadiene by subjecting it tohydrogen from one molecule of the dimer to imother, resulting in the formation of ethyl benzene, ethyl eyclohexane and styrene. The ethyl benzene and ethyl cyclohexane may thereafter be recycled together or separately to the process or to another step where they are aromatlzed under different conditions in the presence of a. contact catalyst, to produce more styrene. In general, however, I prefer to employ conditions at which oleilnle unsaturation is unaiected by hyl0 ucts-and recycling said ethyl benzene to the drogen. Such conditions involve, in general, the use oi' high temperature and short contact time.

Having thus described my invention what I claim is:

The process ot making styrene which coml5 polymerization conditions, separating from the polymerization products a butadiene dimer traetion. aromatizing said butadiene dimerfraction by treating it with an aromatization catalyst at a temperature of about 45o to soo? c. and a space velocity of about 1 to 10 volumes of dimer frac'd tion per hour per volume of catalyst whereby said dimer is converted into styrene and ethyl benzene, recovering styrene from the reaction prodaromatization operation.

VANDERVEER. voonms. 

